Treatment of hydrocarbon oils



'40 the invention, other borates of sufficient solu- .tions has been found effective in reducing polym- 100 50 the invention a treatment of cracked vapors of 110 1.3 approximate gasoline boiling point range from a ll 2& A 3% plant operating upon Pennsylvania fuel oil may 1 811 be considered. Such vapors, arising from the pri- 22 1% mary fractionator of the cracking plant, may be 65 19.9 under a temperature of approximately 275 F. and 1 15 g8 g: a pressure of 60 pounds per square inch. By passl J 90 4012 ing these vapors upwardly countercurrent to an approximately 60% borax solution (corresponding 7 60 since the solubility increases markedly with operation) a treatment of the vapors may be ef- 120 Patented Feb. 6, 1934 I I UNITED STATES PATEL?! OF ICE.

1,946,096 TREATMENT OF HYDROCARBON OILS No Drawing. Application March 25, 1932 Serial No. 601,297

3 Claims. (01. 196-36) This invention relates more particularly to the the temperature, fairly concentrated solutions are treatment of relatively low boiling cracked hyutilizable, since the treatments are ordinarily drocarbons although similar hydrocarbon mixconducted at the elevated temperatures corretures produced in the straight-run distillation of sponding to the mean boiling point of the hy- 6 crude oils and from other sources may also be drocarbon fractions of approximately motor fuel treated by the process. boiling point range evolved from the fractiona- More specifically the invention is concerned tors of cracking plants. Thus treatments may with a process'for treating and refining hydrobe applied at temperatures between the approxicarbon oil mixtures of approximate motor fuel mate range of 250 to 600 F. and pressures from 10 boiling range while in heated vaporous condiatmospheric to several hundred pounds per square tion, the process being peculiarly adapted to proinch may be employed whenever advantageous duce primarily treating effects leading to stafrom an operating standpoint or when necesbilization of such distillates and also to regensary to obtain the optimum temperature of treaterate the desirable properties which may have ment. When relatively high temperatures are 15 been lost on prolonged storage. Cracked hydrofound by trial to be preferable the higher pres- I carbon oils are characterized by the presence of sures may be employed, whereas if only moderl undesirable amounts of gum-forming hydrocarate'temperatures are found to be the best in any bons. particular case, it may at times even be worth The present invention is directed toward more while to conduct treatments under substantial 20 selective removal of the gum-forming constitusub-atmospheric pressures, under which condiso ents and in one specific embodiment comprises tions temperatures as low as 100 to 150 F. may the treatment of hydrocarbon oil vapors in heatbe utilizable, with corresponding modification in ed vaporous condition with aqueous solutions or the treating effects produced. borates. The process requires only simple treating equip- 25 The most generally known member of the class ment such as vertical treating towers containing 5 of compounds known as borates issodium tetrasome type of inert spacing material through borate (NAzBrOmlOHr'O) ordinarily known as which the vapors to be treated may be passed upborax, although analogous compounds of the wardly counter-current to descending streams of other alkaline metals are known and also other treating solutions introduced above the filling ma- 30 compounds with sodium such as, for example, the terial. When more accurate control is desired the metaborate (NABO2.4H2O), which is readily obtower may be provided with regularly spaced trays tained by fusing together the necessary proporsuch as bubble trays or different types of bailies'. tions of boric acid and sodium carbonate. Acid To prevent undue concentration of they solution borates may be employed and may be produced with attendant precipitation of solid salts and 35 by fusing mixtures of borax and boron trioxide, possible clogging or channeling in the treater, regand perborates may also be employed. ulated amounts of steam may be mixed with the While considerations of cost and availability vapors undergoing treatment to increase the parwill usually dictate the use of borax solutions in tial pressure of the water-vapor above the solution. the treatments comprised within the scope of The use of strong borax or other borate solubility may be used, alone or in combination there- 'erizable constituents and resinous materials, I with, when found advantageous. The following therebyimproving the. color and stability ofthe table shows the solubility of borax in water at gasoline and may also haveasubstantial effect upvarying temperatures, the figures given indicaton the sulphur content. The treatment is also 45 ing the amount of anhydrous borax dissolved by especially adaptable t thetrQtment or deterio- 5V parts by weight of water. rated gasolines to restore their original properties as regards low gum content and high knock rating. 1 Among the examples of results obtainable by the Tempsem Solubility 7 ture use of borate solutions according to the process of to a saturated solution under the conditions of 2 fected as indicated by the change in properties evident by consideration of the ,untreated and treated columns in the following tabulation,

the untreated column showing the quality of gaso-' line producible by simple fractionation without vapor phase treatment.

Untreated Treated Gravity "A. P. L 60. 8 61 End point F 425 423 Color, Saybolt 14 29 Color after 4 hrs. exposure to sunl ht 6 24 Gums by copper dish 210 15 Total sulphur 0. l4 0. 09 Octane number 71 From the preceding example it will be apparent that the color, color stability and gum content have been substantially improved, and when it is considered that the total amount of borax solution may be as low as thatequivalent to 3 pounds of borax per barrel of finished gasoline, it will be seen that the process possesses definite advantages, particularly due to the fact that the gasoline'has been stabilized without loss of antiknock value.

As already intimated earlier in the specification, the process may be employed to regenerate the original quality of cracked gasolines which have deteriorated upon long storage. As a characteristic example of this phase of the invention, a tabulation may be given to show the properties of a Pennsylvania acid treated cracked gasoline compared with its properties after 7 months storage and with the properties of a rerunning the stored material against a solution of borax at the rate of two pounds per barrel by the countercurrent method disclosed in the'first example.

REGENERATION Tssrs 3 /2# acid treated Pennsylvania gasoline stored 7 gasoline made by subjecting the said While the general effect of the treatment is evident from a consideration of the table, it may be specially noted that owing to losses of light ends on storage the octane number would be lower even though no other changes had occurred in the gasoline. It is also to be noted that the color is higher and the gum content lower than the gasoline produced by simple redistillation of the stored product, these results also showing the eifect'of the borax treatment.

The foregoing specification andexamples have described the process of the present invention and shown its value as a treating method, but neither the specification nor the numerical data given are to be construed as imposing corresponding narrow limitations upon the generally broad scope of the invention. I

I claim as my invention:

1. A process for refining hydrocarbon oil to remove gum and gum-forming components therefrom, which comprises subjecting the said-hydrocarbon oil while in heated'vaporous condition to the action of an aqueous solution of a water soluble borate, and adding steam to the vapors to prevent undue concentration'of the solution.

2. A process for refining cracked hydrocarbon oil for the purpose of removing gum and gum forming components therefrom, which comprises subjecting the said hydrocarbon oil while in heated vaporous condition to the action of an aqueous solution of a water soluble borate, and addingsteam to the vapors to prevent undue concentration of the solution.

3. A process for refining cracked hydrocarbon oil for the purpose of removing gum and gum forming componentstherefrom, which comprises hydrocarbon oil while in heated vaporous condition'to the action-of an aqueous solution of a sodium tetraborate; and

adding steam to the vapors to prevent undue months Stored Rerun Original Steam Properties gasoline fgfgggf distilled g gg Gravity, A. P. I 59.4 56. 0 68.4 58. 2 Color, Saybo1t 30 3 7 26 Gu n, Mg./ cc copper dish 33 1,060 63 30 Octane number 71 46 65 '65 I 100 A. S. T M. distillation I. B. P. F 114 133 135 136 5" 134 161 160 161 10 156 176 174 176 20 0 190 202 197 199 60% 255 266 257 260 90% 327 334 325 326 E. P. "F 347 361 347 350 over on steam still 93 93 Yrs- 

